Method for preparing polyalkenamers

ABSTRACT

A method for the preparation of polyalkenamer which comprises in an polymerization with ring opening of the alicyclic unsaturated compound in the presence of a catalyst comprising three components: 
     A. a compound of a transition metal of Groups IV-VIII of the Periodic System; 
     B. a compound of a metal of Groups I-VI of the Periodic System; and 
     C. quinone or its halogen derivative or an acid halide of sulfur-containing acid having the general formula R k  SO n  Q t  wherein R is halogen, aryl, alkyl, nitro- or amino-group; S can be sulfur; O represents oxygen; Q stands for halogen; k = 0-1; n = 1-2; t = 1-2; The aforespecified component c makes the catalyst more active.

This invention relates to methods for the preparation of polyalkenamerswhich may find wide application in the synthetic rubber industry.Vulcanizates of the said polyalkenamers have good physicalcharacteristics and elasticity and also good resistance to frost.

There is known a method of preparing polyalkenamers by polymerizationwith ring opening of alicyclic unsaturated compounds in the presence ofa catalytic system comprising a τ-allylic complex of a transition metalof Groups IV-VIII of the Periodic System having the general formula:

    | A.sub.n M.sub.1 X.sub.p L.sub.k |.sub.m

Wherein:

M₁ is a metal of Groups IV-VIII of the Periodic System,

X can be halogen, acetate, hydroxyl, alkoxyl, cyanide, cyclopentadienyl,acetylacetonate, alkyl- and arylsulfonate group.

L represents carbonyl, cyclopentadienyl, cyclooctadiene, benzene,cycloheptatriene, cyclododecatriene, trihalogenphosphine,triphenylphosphine and triphenylphosphite,

A designates a τ-allylic ligand of the general formula ##EQU1## WHEREINR¹, R², R³, R⁴, R⁵, are hydrogen, halogen, alkyl, cycloalkyl and arylhaving from 1 to 10 carbon atoms:

n=0-4; p=0-3; k=0-6; m=1-2; q=1-9;

Taken in combination with compounds of metals of Groups I-VI of thePeriodic System of the general formula

    | M.sub.3 U.sub.d Z.sub.e |.sub.g . P.sub.f

Wherein:

M₃ is a metal of Groups I-VI of the Periodic System,

U -can be hydrogen, halogen and alkoxy-group,

Z represents halogen, aliphatic and aromatic substituent having from 1to 18 carbon atoms;

P stands for ether or amine;

d=0-4; e=0-4; g=1-2; f=0-2

(U.S. Pat. No. 3,660,369).

A method also is known for the preparation of polyalkenamers which usesa catalyst consisting of the salt of molybdenum or tungsten having thegeneral formula

    | M.sub.2 R.sub.a X.sub.b | . Y.sub.c

wherein:

M₂ is molybdenum, tungsten;

R can be halogen, aliphatic and aromatic substituent having from 1 to 10carbon atoms;

X represents halogen, acyl- alkoxy-, aryloxy- and acetylacetonate group;

Y stands for ether or amine;

a=0-6; b=0-6; c=0-3;

a+b=a valence of M₂ metal.

taken in combination with an organic compound or hydride of a metal ofGroups II-III of the Periodic System in the presence of an activatorwhich can be an oxygen-containing compound having O--O or O--H bond(U.S. Pat. No. 3,449,310).

The disadvantage of the known methods is the relatively low activity ofthe catalysts used.

It is the principal object of the present invention to provide a methodensuring a considerable gain in the rate of polymerization and theincreased yield of polyalkenamers.

This and others objects are attained by the method which in accordancewith the present invention consists in the polymerization with ringopening of alicyclic unsaturated compounds having from 4 to 5 and from 7to 12 carbon atoms and from 1 to 4 double bonds in a ring in thepresence of a catalyst comprising

a. a transition metal compound of the general formula

    | A.sub.n M.sub.1 X.sub.p L.sub.k |.sub.m

wherein:

M₁ is a transition metal of Groups IV-VIII of the Periodic System;

X is a ligand selected from the group consisting of halogen, acetate,hydroxyl, alkoxyl, cyanide, cyclopentadienyl, acetylacetonate, alkyl- orarylsulfonate group;

L represents a ligand selected from the group consisting of carbonyl,cyclopentadienyl, cyclooctadiene, benzene, cycloheptatriene,cyclododecatriene, trihalogenphosphine, triphenylphosphine,triphenylphosphite;

A stands for a ligand of the general formula ##EQU2## wherein R¹, R²,R³, R⁴, R⁵ are hydrogen, halogen, alkyl, cycloalkyl, aryl having from 1to 10 carbon atoms;

n=0-4; p=0-3; k=0-6; m=1-2; q=1-9;

or transition metal compounds of the general formula

    | M.sub.2 R.sub.a X.sub.b | .Y.sub.c

wherein:

M₂ is molybdenum or tungsten;

R is halogen, aliphatic and aromatic ligand having from 1 to 10 carbonatoms;

X represents halogen, acyl-, alkoxy-, aryloxy-, and acetylacetonategroup;

Y stands for ether or tertiary amine;

a=0-6; b=0-6; c=0-3;

a+b=a valence of M₂ metal; b. a metal compound having the generalformula

    |M.sub.3 U.sub.d Z.sub.e |.sub.g .P.sub.f

wherein:

M₃ is a metal of Groups I-VI of the Periodic System;

U is hydrogen, halogen, alkoxy-group;

Z represents halogen, aliphatic or aromatic radical having from 1 to 18carbon atoms;

P stands for ether or amine;

d=0-4; e=0-4; g=1-2; f=0-2;

d+e=a valence of M₃ metal;

c. an activator selected from ortho-benzoquinone, para-benzoquinone,naphthaquinone, anthraquinone, phenanthrenequinone, their fluoro-,chloro-, promo-, iodo-derivatives or an acid halide of sulfur-containingacid having the general formula

    R.sub.k SO.sub.n Q.sub.t

wherein:

R is halogen, aryl-, alkyl-, nitro- and amino-group;

S can be sulfur;

O represents oxygen;

Q stands for halogen;

k=0-1; n=1-2; t=1-2.

Substituents in the ring of an alicyclic compound may be alkyl-, aryl-,aralcyl-, alkaryl-, acyl-, alkoxy-group having from 1 to 10 carbon atomsand also halogen atoms. The ring of an alicyclic compound may have oneor more such groups or atoms.

Polymerization may be carried out in an inert solvent such as aliphatic,alicyclic, aromatic hydrocarbon, their halogenated derivative or etherfor 0,1 up to 10 hrs at a temperature of from -50° to +80°C.

The molar ratio of the monomer and the transition metal compound may befrom 100 to 20,000.

The molar ratio of the catalyst components a:b:c may be 1:|0.1-50|:|0.1- 10|.

The proposed method for the preparation of polyalkenamers is realized inthe following manner.

Polymerization is carried out as a continuous or batch process inreactors of conventional type which are usually used e.g. for thepolymerization of butadiene or isoprene. The aforespecified componentsmay be introduced in a solution simultaneously or one after another. Theresultant polymer may be isolated from a solution by any conventionalmethod, e.g. by precipitation with ethanol.

The above-identified catalytic systems used in the polymerizationaccording to the proposed method are characterized by increased activityas compared to known catalysts.

The employment of quinones, their halogen derivatives and acid halidesof sulfur-containing acid as an activator increases in the rate ofpolymerization and also the conversion of monomers.

The aforespecified activators are readily available commercial products.In use in the proposed method such activators provide reproducibleresults.

For a better understanding of the present invention the proposed methodwill now be described by way of illustration in the following examples.

EXAMPLE 1

Into a 100-ml., round-bottomed, three-necked flask are placed underargon 45 ml. of toluene, 10g of cyclopentene, 15×10.sup.⁻⁵ mole of WCl₆in 4 ml. of toluene, 15×10.sup.⁻⁵ mole of para-benzoquinone in 2 ml. oftoluene, and 6×10.sup.⁻⁴ mole of ethylaluminium dichloride. Thepolymerization is carried out at a temperature of 0°C for a period of 2hours. The polymer is obtained in a yield of 6.5 g. (65% of thetheoretical amount). The polymer contains the theoretical number ofdouble bonds; its intrinsic viscosity |η |=3.5 dl./g. (in benzene, at25°C).

EXAMPLE 2

The polymerization is carried out as described in Example 1, except thattungsten oxytetrachloride/diisobutylaluminiumchloride/tetrachloroquinone in the molar ratio of 1/1/0.25 is used asthe catalyst system. Cyclooctene is used as the monomer.

After 1 hour, the polymer is obtained in a yield of 93% of thetheoretical amount; its intrinsic viscosity |η |=2.05 dl./g. (inbenzene, at 25°C).

EXAMPLE 3

The polymerization is carried out as described in Example 1, except thathexaphenoxytungsten/tetraethyltin/tetrafluoroquinone (the molar ratio1/2/0.5) in a chlorobenzene solution is used as the catalyst system.Cyclobutene is used as the monomer.

After 5 minutes, the polymer is obtained in a yield of 100% of thetheoretical amount; its intrinsic viscosity |η |=3.2 dl./g. (in benzene,at 25°C).

EXAMPLE 4

The polymerization is carried out as described in Example 1, except thatchloroethoxytungsten pentachloride/diethylzinc/benzoquinone in a benzenesolution is used as the catalyst system. As a monomer, cis,trans-cyclodecadiene -1,5 is used.

After 4 hours the polymer is obtained in a yield of 72% of thetheoretical amount; its intrinsic viscosity |η |=1.65 dl./g. (inbenzene, at 25°C).

EXAMPLE 5

The polymerization is carried out as described in Example 1, except thatdioxo(acetylacetonate)molybdenum/diethylaluminiumchloride/1.4-naphtaquinone in a cyclohexane solution is used as thecatalyst system. As a monomer 3-phenylcyclooctene is used.

After 8 hours the polymer is obtained in a yield of 47% of thetheoretical amount; its intrinsic viscosity |η |=1.25 dl./g. (inbenzene, at 25°C).

EXAMPLE 6

The polymerization is carried out as described in Example 1, except thatMoOCl₃.dipyridyl/HAlCl₂.trimethylamine/dibromoquinone (the molar ratio1/4/1) in a heptane solution is used as the catalyst system. As amonomer 1-methylcyclooctadiene-1,5 is used.

After 3 hours the polymer is obtained 1, a yield of (the of thetheoretical amount; its intrinsic viscosity |η |=2.2 dl./g. (in benzene,at 25°C).

EXAMPLE 7

The polymerization is carried out as described in Example 1, except thattungsten hexachloride/butyllithium/chloranil (the molar ratio 1/3/4) ina toluene solution is used as the catalyst system.

The catalyst complex is prepared in the presence of the monomer, cis,trans, trans-cyclododecatriene-1,5,9. After 2 hours the polymer isobtained in a yield of 78% of the theoretical amount; its intrinsicviscosity |η |=1.57 dl./g. (in benzene, at 25°C).

EXAMPLE 8

Into a 50-l., stainless steel autoclave fitted with a stirrer and ajacket are fed 30l. of benzine, 6l. of cyclopentene, 13.5×10.sup.⁻³ moleof tungsten hexachloride, 13.5×10.sup.⁻³ mole of para-benzoquinone, and54×10.sup.⁻³ mole of ethylaluminium dichloride. The polymerization iscarried out at a temperature of -5°C for a period of 3 hours.

The polymer is obtained in a yield of 70%. The intrinsic viscosity ofthe polymer |η |=3 dl./g. (in benzene, at 25°C); its glass transitiontemperature T_(g) = -102°C.

EXAMPLE 9

Into a 100-ml., round-bottomed, three-necked flask are placed underargon 45ml. of toluene and 10g. of cyclopentene, 15×10.sup.⁻⁵ mole oftungsten hexachloride in 4 ml. of toluene, 15×10.sup.⁻⁵ mole ofbenzenesulfochloride in 2 ml. of toluene and 6×10.sup.⁻⁴ mole ofethylaluminium dichloride in 2 ml. of toluene. The polymerization iscarried out at a temperature of 0°C for a period of 0.2 hour. Thepolymer is obtained in a yield of 6g. (60% of the theoretical amount).

The polymer contains the theoretical amount of double bonds. Theintrinsic viscosity of the polymer |η |=2.43 dl./g. (in benzene, at25°C).

EXAMPLE 10

The polymerization is carried out as described in Example 1, except thattungstenoxytetrachloride/diisobutylaluminiumchloride/benzenesulfinylchloride in the molar ratio of 1/1/0.25 is usedas the catalyst system. As a monomer cyclooctene is used. After 1 hourthe polymer is obtained in a yield of 85% of the theoretical amount; itsintrinsic viscosity |η |=1.9 dl./g. (in benzene, at 25°C).

EXAMPLE 11

The polymerization is carried out as described in Example 1, except thattris(phenoxy)molybdenum chloride/H₂ AlI.diethyl ether/thionyl chloride(the molar ratio 1/2/1) in a heptane solution is used as the catalystsystem. As a monomer cyclobutene is used.

After 0.5 hour the polymer is obtained in a yield of 92% of thetheoretical amount; its intrinsic viscosity |η |=2.85 dl./g. (inbenzene, at 25°C).

EXAMPLE 12

The polymerization is carried out as described in Example 1, except thattungsten hexafluoride/tetraethyltin/sulfuryl chloride (the molar ratio1/2/0.25) in a chlorobenzene solution is used as the catalyst system. Asa monomer cis, trans-cyclodecadiene-1,5 is used.

After 5 hours the polymer is obtained in a yield of 65% of thetheoretical amount; its intrinsic viscosity |η |=1.95 dl./g. (inbenzene, at 25°C).

EXAMPLE 13

The polymerization is carried out as described in Example 1, except thatchloroethoxytungsten pentachloride/butyllithium/parabromobenzenesulfochloride (the molar ratio 1/2/0.5) in a benzene solution is used asthe catalyst system. As a monomer 3-phenylcyclooctene is used.

After 10 hours the polymer is obtained in a yield of 52% of thetheoretical amount; its intrinsic viscosity |η |=1.07 dl./g. (inbenzene, at 25°C).

EXAMPLE 14

The polymerization is carried out as described in Example 1, except thatthe combination dioxoacetylacetonatemolybdenum/triethylaluminium/p-aminobenzenesulfochloride (the molarratio 1/1/1) in a toluene solution is used as the catalyst system. As amonomer 1-methylcyclooctadiene-1,5 is used.

After 1.5 hour the polymer is obtained in a yield of 25% of thetheoretical amount; its intrinsic viscosity |η |=1.7 dl./g. (in benzene,at 25°C).

EXAMPLE 15

The polymerization is carried out as described in Example 1, except thattungsten hexachloride/diethylaluminium chloride/m-xylene-4-sulfochloride(the molar ratio 1/3/1) in a chlorobenzene solution is used as thecatalyst system. As a monomer cis, trans, trans-cyclododecatriene-1,5,9is used.

After 5 hours the polymer is obtained in a yield of 65% of thetheoretical amount; its intrinsic viscosity |η |=2.05 dl./g. (inbenzene, at 25°C).

EXAMPLE 16

The polymerization is carried out as described in Example 1, except thatcyclohexenesulfochloride is used as the activator. After 0.5 hour thepolymer is obtained in a yield of 58% of the theoretical amount; itsintrinsic viscosity |η |=2.20 dl./g. (in benzene, at 25°C).

EXAMPLE 17

The polymerization is carried out as described in Example 1, except thatpropanesulfochloride is used as the activator.

After 1 hour the polymer is obtained in a yield of 62% of thetheoretical amount; its intrinsic viscosity |η |=2.02 dl./g. (inbenzene, at 25°C).

EXAMPLE 18

a. Into a 100-ml., round-bottomed, three-necked flask are placed 65 ml.of benzene, 0.15×10.sup.⁻³ mole of tetra (τ -pentenyl)tungsten in 2 ml.of benzene, 0.15×10.sup.⁻³ mole of benzoquinone in 2 ml. of benzene,0.30×10.sup.⁻³ mole of aluminium bromide in 1 ml. of benzene, and 10g.(15×10.sup.⁻² mole) of cyclopentene.

The polymerization is carried out at temperature of 0°C for a period of1 hour. The polymer is obtained in a yield of 8.5g. (85% of thetheoretical amount). The polymer contains the theoretical amount ofdouble bonds.

The intrinsic viscosity of the polymer |η |=2.5 dl./g. (in benzene, at25°C).

b. The polymerization of cyclopentene is carried out in the absence ofthe activator. Into a reaction flask are placed 0.375×10.sup.⁻³ mole oftetra-(τ -crotyl)tungsten, 0.75×10.sup.⁻³ mole of aluminium bromide, 7.7g. (11×10.sup.⁻² mole) of cyclopentene. After a period of 5 hours at atemperature of 30°C the polymer is obtained in a yield of 90% (the checkrun).

EXAMPLE 19

The polymerization is carried out as described in Example 1, except thattetra(τ -allyl)zirconium/dichloroquinone/tungsten hexachloride in themolar ratio of 1/1/4 is used as the catalyst system.

After 1.5 hour the polymer is obtained in a yield of 73% of thetheoretical amount; its intrinsic viscosity |η |=1.78 dl./g. (inbenzene, at 25°C).

EXAMPLE 20

The polymerization is carried out as described in Example 18, exceptthat tetra(τ -methallyl)tungsten/tetraiodoquinone/diethylethoxyaluminium(the molar ratio 1/1.5/4) in a toluene solution is used as the catalystsystem. As a monomer cis-cyclooctene is used. After 1 hour the polymeris obtained in a yield of 92% of the theoretical amount. Its intrinsicviscosity |η |=3.0 dl./g. (in benzene, at 25°C).

EXAMPLE 21

The polymerization is carried out as described in Example 18, exceptthat cyclopentadienylcobalt dicarbonyl/1,4-naphtaquinone/tungstenhexafluoride (the molar ratio 1/1/2) in a heptane solution is used asthe catalyst system. After 0.5 hour the polymer is obtained in a yieldof 95% of the theoretical amount; its intrinsic viscosity |η |=4.2dl./g. (in benzene, at 25°C).

EXAMPLE 22

The polymerization is carried out as described in Example 18, exceptthat cyclopentadienyltantalum tetracarbonyl/triethylaluminium/chloranil(the molar ratio 1/0.5/4) in a toluene solution is used as the catalystsystem. As a monomer 1-methylcyclooctadiene-1,5 is used. After 5,5 hoursthe polymer is obtained in a yield of 40% of the theoretical amount; itsintrinsic viscosity |η |=1,47 dl./g. (in benzene, at 25°C).

EXAMPLE 23

The polymerization is carried out as described in Example 18, exceptthat Re₂ (CO)₁₀ /o-benzoquinone/tetraphenyltin (the molar ratio 1/1/3)in a benzene solution is used as the catalyst system. As a monomer cis,trans, trans-cyclododecatriene-1,5,9 is used. After 5 hours the polymeris obtained in a yield of 56% of the theoretical amount; its intrinsicviscosity |η |=1,27 dl./g. (in benzene, at 25°C).

EXAMPLE 24

The polymerization is carried out as described in Example 18, exceptthat bis(τ -allyl)nickel/phenyltungsten pentachloride/2,5-dibromoquinone(the molar ratio 1/4/1,5) in a cyclohexane solution is used as thecatalyst system. As a monomer 3-phenylcyclooctene is used. After 4 hoursthe polymer is obtained in a yield of 51% of the theoretical amount; itsintrinsic viscosity |η |=1,38 dl./g. (in benzene, at 25°C).

EXAMPLE 25

The polymerization is carried out as described in Example 18, exceptthat tris(τ -crotyl)tungsten chloride/benzoquinone/a complex ofchloralan with trimethylamine (the molar ratio 1/1/2) in a chlorobenzenesolution is used as the catalyst system. As a monomer cis,trans-cyclodecadiene-1,5 is used. After 6 hours the polymer is obtainedin a yield of 73% of the theoretical amount; its intrinsic viscosity |η|=1,85 dl./g. (in benzene, at 25°C).

EXAMPLE 26

a. Into a 100-ml., round-bottomed, three-necked flask are placed 65 ml.of benzene, 0.15×10.sup.⁻³ mole of tetra (τ - methallyl)tungsten in 2ml. of benzene, 0.15×10.sup.⁻³ mole of thionyl chloride in 2 ml. ofbenzene, 0.6×10.sup.⁻³ mole of aluminium bromide in 1 ml. of benzene and1og. (15×10.sup.⁻² mole) of cyclopentene. The polymerization is carriedout at a temperature of 0°C for a period of 0.5 hour. The polymer isobtained in a yield of 8.7 g (87% of the theoretical amount). Thepolymer contains the theoretical amount of double bonds; its intrinsicviscosity |η |=2,3 dl./g. (in benzene, at 25°C).

b. The polymerization of cyclopentene is carried out in the absence ofthe activator, the monomer to τ-complex ratio being 300/1. After aperiod of 5 hours at a temperature of 30°C the polymer is obtained in ayield of 90% (the check run).

EXAMPLE 27

The polymerization is carried out as described in Example 26, exceptthat tetra(τ -allyl)zirconium/benzenesulfochloride/tungsten hexachloridein the ratio of 1/1/4 is used as the catalyst system. After 0.2 hour thepolymer is obtained in a yield of 75% of the theoretical amount; itsintrinsic viscosity |η|=1,80 dl./g. (in benzene, at 25°C).

EXAMPLE 28

The polymerization is carried out as described in Example 26, exceptthat tetra (τ -pentenyl)tungsten/benzenesulfinyl chloride/diethylethoxyaluminium (the molar ratio:1/1,5/4) in a toluene solution is used as thecatalyst system. As a monomer cis-cylooctene is used. After 1 hour thepolymer is obtained in a yield of 90% of the theoretical amount; itsintrinsic viscosity |η |=3,o dl./g. (in benzene, at 25°C).

EXAMPLE 29

The polymerization is carried out as described in Example 26, exceptthat cyclopentadienylcobalt dicarbonyl/sulfuryl chloride/tungstenhexafluoride (the molar ratio 1/1/2) in a heptane solution is used asthe catalyst system. As a monomer cyclobutene is used. After 0.5 hourthe polymer is obtained in a yield of 95% of the theoretical amount; itsintrinsic viscosity |η |=4.5 dl./g. (in benzene, at 25°C).

EXAMPLE 30

The polymerization is carried out as described in Example 26, exceptthat cyclopentadienyltantalumtetracarbonyl/parabromobenzenesulfochloride/ethylaluminium dichloride(the molar ratio 1/1.5/4) in a chlorobenzene solution is used as thecatalyst system. As a monomer cyclooctadiene-1,5 is used. After 1.5 hourthe polymer is obtained in a yield of 73% of the theoretical amount; itsintrinsic viscosity |η|=1.85 dl./g. (in benzene, at 25°C).

EXAMPLE 31

The polymerization is carried out as described in Example 26, exceptthat dirheniumdecacarbonyl/para-aminobenzenesulfochloride/phenyltungsten pentachloride(the molar ratio 1/0.5/2) in a toluene solution is used as the catalystsystem. As a monomer cyclopentene is used. After 2 hours the polymer isobtained in a yield of 50% of the theoretical amount; its intrinsicviscosity |η|=1.75 dl./g. (in benzene, at 25°C).

EXAMPLE 32

The polymerization is carried out as described in Example 26, exceptthat tris(τ -allyl)tungsten chloride/thionyl chloride /a complex ofchloralan with trimethylamine (the molar ratio 1/1/4) in a cyclohexanesolution is used as the catalyst system. As a monomer cis, trans,trans-cyclododecatriene-1,5,9 is used. After 1 hour the polymer isobtained in a yield of 80% of the theoretical amount; its intrinsicviscosity |η|=1,2 dl./g. (in benzene, at 25°C).

We claim:
 1. A method for the preparation of a polyalkenamer byhomopolymerization comprising subjecting an alicyclic unsaturatedcompound having from 4 to 5 and 7 to 12 carbon atoms and from 1 to 4double bonds in the ring to polymerization with ring opening in thepresence of a catalyst consisting of three components: a) a compoundselected from the group of a transition metal compound comprisingτ-complexes of transition metals having the general formula

    | A.sub.n M.sub.1 X.sub.p L.sub.k |.sub.m

wherein: M₁ is a transition metal selected from groups IV-VIII of thePeriodic System; X is a ligand selected from the group consisting ofhalogen, acetate, alkoxyl, cyanide, cyclopentadienyl, acetylacetonate,alkyl- and arylsulfonate group; L represents a ligand selected from thegroup consisting of carbonyl, cyclopentadienyl, cyclooctadiene, benzene,cycloheptatriene, cyclododecatriene, trihalogenphosphine,triphenylphosphine, triphenylphosphite; A stands for a ligand selectedfrom τ-allylic ligands having the general formula ##EQU3## wherein:R¹,R²,R³,R⁴,R⁵ are ligands selected from the group consisting ofhydrogen, halogen, alkyl, cyanoalkyl and aryl having from 1 to 10 carbonatoms;n=0-4; p=0-3; k=0-6; m=1-2; q=1-9;and transition metal compoundsof the general formula

    |M.sub.2 R.sub.a X.sub.b | Y.sub.c

wherein: M₂ is molybdenum or tungsten; R is a ligand selected from agroup consisting of halogen, aliphatic and aromatic substituent havingfrom 1 to 10 carbon atoms; X represents a ligand selected from a groupconsisting of halogen, acyl, alkoxy-, aryloxy- and acetylacetonategroups; Y stands for a ligand selected from the group comprising etherand amine;a=0-6; b=0-6; c=0-3; a + b = a valence of M₂ metal; b. acompound of a metal selected from Groups I-VI of the Periodic Systemhaving the general formula |M₃ U_(d) Z_(e) |_(g) P_(f) wherein: M₃ is ametal selected from Groups I-VI of the Periodic System; U is a ligandselected from the group consisting of hydrogen, halogen andalkoxy-group; Z represents a ligand selected from the group consistingof halogen, aliphatic and aromatic ligands having from 1 to 18 carbonatoms; P stands for a ligand selected from the group comprising etherand amine;d = 0-4; e = 0-4; g = 1-2; f = 0-2; and c. an activatorselected from the group consisting of quinones, halogenated quinones andan acid halide of sulfur-containing acid having the general formula

    |R.sub.k SO.sub.n Q.sub.t |

wherein: R is a ligand selected from the group consisting of halogen,alkyl, aryl, nitro- and amino-group; Q is a ligand selected from thegroup of halogens; S represents sulfur; O stands for oxygen;k = 0-1; n =1-2; t = 1-2; wherein the molar ratio of the catalyst components a:b:cis 1:0.1-50:0.1-10, and the molar ratio of the monomer to the transitionmetal compound is within the limits 100-20,000:1.
 2. A method accordingto claim 1 wherein the polymerization process is carried out in an inertsolvent selected from the group consisting of hydrocarbons, halogenatedhydrocarbons and ethers.